Manufacture of dyestuffs containing metal



Patented Oct. 21, 1930 UNITED "STATES PATENT oFFlca Fnr'rz s'mAcB, JOSEPH aim, Ann o'rrro'xzusnn, OEBASEL, SWITZERLAND, ASSIGNORS T0 socIE'rY or CHEMICAL INDUSTRY IN BAsLE, or BASEL, SWITZERLAND o 'MANUFACTURE or DYESTUFFSCON'IIAINING METAL No Drawing. Application filed October 1, 192a, S eria1"N'o.'-309,588, and in Switzerland October 8, 1927'.

In the fundamental specification No.

1,667,312 there is described the manufacture the cyanuric halide, and the relative proportions of the reactants, there may be obtained by the invention products resulting from the replacement of one or more halogen atoms of a cyanuric halide by a residue of an azo-dyestuff containing metal; or products resulting from the replacement oftwo or more halogen atoms of a cyanuric halide by residues of two or more different azo-dyestuffs containing metal; or products resulting from the replacement of one or more halogen atoms of a cyanuric halide by a residue of an azoedyestuff containingv metal, and of another or other halogen atoms of the cyanuric halide by a residue of an azo-dyestufi not containing metal or by another residue containing a chromop'horic -group or groups, or not containing achromophonc group.

The metal compounds which are used in the -manufacture in accordance with the invention may be derived from any metal which is capable of combining with mordant dyeing dyestufis, (of. the numerous literature in this connection). I As in the aforesaid specificationthe products obtainable'in accordance'with the inven; tion may be subjected to a further treatment,

such as coupling with a diaZo-compound or diazotization 'andifurther coupling in substance or on the fibre, reduction, condensation, acidylatlon (which includes treatment with phosgene), alkylation, aralkylation, arylaw Aisolution of the'copper compound from 43.9 parts of the azo-dyestuff from diazotiz-ed 2-amino-1-phenol-4-sulfonic acid and 2-amino5- hydroxynaphthalene 7 sulfonic acid (coupled in alkaline solution) is added to a suspension of 18.4 parts of cyanuric chloride in 1 litre of icecold water, and the from 1 molecular proportion of cyanuric chloride and 1 molecular proportion of the aforesaid aao-dyestutl containing copper obtained accordingly to the equation soar H is produced. The dyestutl is separated by filtration; it dyes cotton, Wool and silk bluishred shades.

Ewample :2

a secondary condensation product from 1 1110-- lecular proportion of cyanuric chloride, 1 molecular proportion of the aforesaid dyestuft containing chromium and l D'iOleClllill' proportion of aniline. The new dyestuil is precipitated by acidifying the reaction mixture; it is a dark, lustrous powder which dyes cotton, W001 and silk blue-grey shades.

Ezmmple 18.4 parts of cyanuric chloride suspendeu in a small quantity of Water a re introduc d into an aqueous solution 011" the chromium compound obtainable by the action of 30.4: parts of Cr O in form of chromium fluoride on 71.8 parts of the dyestuii from diazotized l-amino-2-hydroxynaphthalene 4 sulfonic acid and meta-aminophenol. The Whole is slowly heated to 40 C. and maintained at this temperature for 2 hours, whereupon the chromium compound of the secoi'idary condensation product from 1 molecular proportion of cyanuric chloride and 2 molecular pro portions of the aforesaid dyestufl' containing chromium is precipitated by the addition of common salt. The dyestuff dyes cotton, Wool and silk grey-Violet tints.

The dyestuff obtained in accordance With this example still contains a chlorine atom capable of being replaced, and it may be can. to react With a further compound containing an OH, SH or NH 'roup, as described in specification No. 1,667,312; for example, 82.9 parts of the product are dissolved in Water, 9.3 parts of aniline added and the whole heated for 1 hour at 80 C., whereby there is formed according to the equation a tertiary condensation product from 1 molecular proportion of cyanuric chloride, 2 molecular proportions of the chromium compound of the dyestuft from diazotized 1-amino-2- hydroxynaphthalene-4-sulfonic acid and ineta-aininophenol and 1 molecular proportion of aniline. The new dyestuff so obtained is a dark powder, Which dyes cotton, Wool and sill: blue-Violet shades.

In like manner there may be made a ter tiary condensation product from 1 molecular proportion oil cyanuric chloride, 2 molecular proportions of the chromium compound of the azo dyestuil obtained. by simultanemis chroming and reduction of the aZo-dyestuft from the nit-rated diam-compound of 1* amino-2-hydroxynaphthalene-hsulfonic acid and l-phenyl-3-methyl-5-pyrazolone (conr pare specification Serial No. 294,056) and 1 molecular proportion of aniline. This dyestufi' dyes cotton, wool and silk red shades. whilst a dyestutl' which dyes cotton, Wool and sill; blue-green shades may be obtained b using for the manufacture of the dyestuii 1-hydroxynaphthalene-8-sulfamide instead of the aforesaid pyrazolone derivative. By

using in the manufacture of the last-named dyestufi 1-chloro-2 4-phenylenediamine' instead of aniline, there is obtained a dyestufi" which can be diazotized on the fibre and developed by. means of B-naphthol.

I The dyestufi' from 1' molecular proportion of cyanuric chloride, 2 molecular proportions of the copper compound of the monoazo-dyestuff from diazotized 2-aminophenol-4-sulfonic acid and 2-amino-8-hydroxynaphthalene-6-s'ulfonic acid and 1 molecular proportion of aniline, dyes cotton, W001 and silk blue-red shades.

Example 4 To a suspension of 18.4 parts of cyanuric chloride in ice-cold ater there is added a neutral solution of the chromium compound obtained by simultaneous chroming and reduction of 182.3 parts of the dyestuif from the nitrated diazo-compound of 1-amino-2' hydroXynaphthalene-4-sulfonic acid and anaphthol, in Which diazo-compound the position of the nitro group is not exactly known. The mixture is stirred first'for 1 hour at O10 6., then for 2 hours at 40 0. and finally for 1 hour at C. The product, which is a tertiary condensation product from 1 molecular proportion of cyanuric chloride and 3 molecular proportions of the aforesaid chromium compound obtainedaccording to the equation r i on is' a dark, lustrous powder; it dyes cotton Wool and silk fast grey tints.

Emample 5 Into an aqueous solution of 38.7 parts of the primary condensation product from'l molecular proportion of cyanuric chloride and 1 molecular proportion of 2-amino-5- hydroxynaphthalene-7-sulfonic acid (obtainable according to specification No. 1,667,312) there is run a solution of the chromium compound obtainable by simultaneously chronr ing and reducing 38.9 parts of the dyestulf from diazotized 6-nitro-2-amino-1-phenol4- sulfonic acid and ,B-naphthol. The mixture is maintained for 2 hours at 40 C. and the product Which has formed according to the equation r is precipitated by addition of acid. It is a dark powder, which dyes cotton, Wool and silk violet shades.

By substituting the remaining chlorine atom in this dyestuff by the 1-chloro-2:4- phenylenediamine residue there is obtained a product Which dyes cotton and silk violet shades and can bediazotized either in substance or on the fibre; a brown red dyeing being produced by diazotizing on the fibre anddeveloping With B-naphthol.

and silk brown red and can be further developed on the fibre by diazotization' and coupling. v

, E wample 6 18.4 parts ofcyanuric chloridein the form of an aqueoussuspension are introduced into an aqueous solution of the copper compound made from 87.8 parts of the dyestufi' from diazotized 2-aminophenol-4-sulfonic acid and 2 amino 8 hydroxynaphthalene 6. sulfonic acid (coupled in alkaline solution). The Whole is maintained for 2 hours at a temperaof 40 C. After Which time 14.2 parts of 1-chloro-2:4-phenylenediamine are introduced in the form of an aqueous solution and the Whole is stirred for a further hour at C. By addition of acid. there is precipifated :I, tertiary condensation product ohtaincd according to the eqruition from 1 inolecuhu' propol'ion ot cyunuric chloride molecular proportmns of the store-- sand c H per compound and. l nioiecuhi-l proportion of 'l-chloro--Q:-cl-;hcnylcnedmnnne. The product is a broY-Jnisli-l, powder which dyes cotton Wool and s1 bluish rec. shades.

on the fihre and ire:v i 7 whereby there are ohtsincc rot. dyeilw's to washing.

Ezra/mph 7 parts of cyanuric ded solution ll om dis zotizeo.

. Whole is maintained for 52 hours at C. The product obtziii ed according to the equation sinnlsr to those above described.

1 sample 8 solution of the clu'oi'uiuln compound 0.9 parts of the dystufli "from diusoti zed. -un1i;.1o-53hydroxynuphthalene-lsul'tonic acid and l.-amino-5-hydroxynaphthslene th re are introduced an aqueous suspension of 18.4 ports of cyanuric chloride and, utter standing for 1 hour, solution of the copper compound made from ot' the dyestu'ff from diszotized l-smino-Q- hjtdrfmynsphthelonesulfonic acid 8-amino-1-phenol and the Whole is stirred at --:5 C. for 2 hours. 9.3 parts of aniline are hen introduced into the reaction mixture and e Whole is maintained at 80 C. for 1 hour. Lie product obtains uccoroing to the equa- 'tion both i copper complex and a chromium complex. It is 3 dark, lustrous po vder and dyes cotton, Wo nd silk violet.

If in ti 1 example, instead of 0.3 parts of aniline there are used 1&2 parts of l-chloro- 2 4-phenylenediamine, there is obtained a tertiary condensation product containing, be-

sides a copper complex and a chromium compleX,fla free amino-group. The new dyestuff is a dark powder which dyes cotton, W001 and silk violet. Y i

The dyeings may be diazotized onthe fibre and subsequently treated with B-naphthol, resorcinol, I or the like; in this manner fastness of the dyeings to washing is improved.

Ew ample .9

Into a suspension of 18.4 parts of cyanuric chloride in 1000 parts ofwater there is introduced a solution of 40.9 parts of a dyestuff containing chromium, which is obtained by combining the diazo-compound of 1-amino-' 2-hydroxynaphthalene-4 sulfonic acid with oc-IIELPhllllOl in presence of an alkali chromite, subjecting the chromium compound thus obtained to nitrosation and reducing the dyestuff thus produced. After the mixture has 7 been stirred for some time there is added a solution of 15 parts of para-aminoacetanilide and the whole is maintained at 50? C. for 2 hours, and is finally stirred for a further hour at 80 C. with 9.3 parts of aniline. The tertiary condensation product obtained according to the equation SOsH 1-phenyl-3-methyl-5pyrazolone stuff, 1 molecular proportion of para-phenylenedia-mine and '1 molecular proportion of aniline. The new disazo-dyestuff containing metal is a dark powder which dyes cotton, wool and silk blue shades.

Ewample 10 There is. prepared in known manner the 7, primary condensation product from 18.4 parts of cyanuric chlorideand 35.9 parts of a I dyestuif containing-chromium which is obtainable by simultaneously chroming and reducingv .the product made by" coupling diazotized 6nitro-2-amino-l-phenol-4-sulfonic acid and fl-naphthol. The product is stirred, together with 5.4 parts of para-phenylenediamine at 40 0. until 10.6 parts of anhydrous sodium carbonate have been used in order to neutraliz'ethe hydrochloric acid which has formed. The reaction mixture is then heated with theaddition of 9.3 parts of aniline for 1 hour at 75 C. and the condensation product Which has formed isprecipitated by the additionof hydrochloric acid. The new dyestufl' obtained according to the equation is a dark powder whichdyes cotton, Wooland :silk violet shades.

A large number of other examples might also be given in illustration of the invention; it is sufiicient, however, in this respect to refer to the numerous combinations which are possible, various types of which will be appreciated from a consideration of the examples .of specification No. 1,667,312.

In the following table isshown the com- 1 position and dyeing properties of a small numberof some further dyestuffs which are obtainable in accordance with the invention l N i D in on X-d J X fippg r g of ye g 10 rie ye- \\N/ stuil wherein 1: is halogen, are condensed with the following component lllCll have renctive hydrogen atoms attached to one of a group of XTlQlJilllOidS comprising 0, S or N:

1st component 2nd component 3rd component W001 Cotton Sill:

Copper compound of the mono- As the first eom- Black powder Yellow-brown Yellow-brown Yellow-brown nzo-d ,vestull from dinzotized 4- ponent sulio-fi-amino -1- plienol-2-carboxylic acid and wnophthylamine Do. do. Aniline do. do. do. ."Do. Copper compound of the mono- As the first com- Dark powder Brown Brown Brown azo-dyestulf from diazotized 4- ponent sulio 6 -nn1ino 1 phenol 2- carboxylic acid and metaflllllHO-XlllCIlOl Do. do. Aniline do, do. do. Do. (upper compound of the mono As the lirst oom- Dark Orange Orange Orange nzo-dyestufl from dizaotized 2 poneni: aminohe'nzoie acid and 2 amino-S-hydroxynaphthalonc- 7-sultonic acid Do do. Porwtoluidine do. do. do. Do. Chromium-compound oi the As the first con1- Ammonia Black powder Violet Violet Violet monoezo-dyestufl from diazoponeut tired tanrinodphenol boxylic acid and 2nznino-5- hydroxynephthalene 7 sulionic acid Chromium-compound oi the As the first eom- '.\l 0110- zncthylarn- Black powder Violet Violet Violet mouoazo-dycstull from diazoponont inc tired 2-an1inobenzoic acid and 2-amino-5-hydr0xynaphtholene-7-sulfonic ncid Chromium compound of para- As the first com- Aniline Brown powder Yellow Yellow Yellow amino-benzene ozosolicylic poncnt Cobnltcompoundoithc reduced As the first com- I-chlQrmQul-phe- Black powder Violet Violet Violet azo-dyestufi from the nitrnted pollent 'i'iylcuediamine diam-compound of l-amino- Zhydroxynophthalene-4-sulionic acid and B-naphthol Nickel coinpound of the reduced As the first corn Aniline Black powder Redwiolet Blue violet Blue-violet monoazo-dyestull from the niponent trated diam-compound of 1- amino-2-hydroxynaphthalene- 4-sulfonic acid and a-nophthol Chromiunncornpound oi the Paro-aniino-ben- Aniline Black powder Green Green Green rnonoazo-dyestuil from (liazozene azosolicylic tized 4-nitro-2-aininophenol nc' and 1amino-2-hydr0xynupln thalene-3:o-disullonic acid Monoazo-dyestufl from diazo- Chromium-corn- Aniline Black powder Green Green Green tized 2-aminonaphthelene-l:8 pound of the redisulfonic mold and cresidine duced mononzo- (methyl ether) dyestufl' from the nitroted dia zo-cornpound of lnrnino 2 hydroxynaphthw lenc l-sulfonic acid and 5:8-dichloro-l-hy droxyna p nth olone l Chromium-coin pound of the sa- Aniline Aniline Black powder Red-violet Rediolet Red-violet ponified mononzo-dyestuil" iroln i-ocet "lamino-2-amino-lphenoi-(l-sulfonic acid and pyrogallol I era amino-hem Yellowish Yellow Yellow Yellow Chromium salt of para-ominosahcyhc acid zene-azosalicylic acid hat we claim is 1. A manufacture of complex metal compounds or azo-(lyestull's containing cyanuric nuclei by condensing; cyztnuric halides with reactive compounds which have nuclei by condensing cyanuric halides congen atoms attached to one oi? a group of metnlloids comprising 0, S or N, at least one of which compounds is complex metal compound of an azo-dyestuif.

2. A. manufacture oi? con'iplex metal compounds of aZo-dyestuiis containing cyonui'lc In witness whereoi we have hereunto signed our names this 19th day of September, i 1.928.

FRITZ STRAUB. JOSEPH syn. OTTO KAISER. 

